Vat dye compositions containing



Patented Mar. 6, 1945.

VAT DYE COMPOSITIONS CONTAINING MIXED DIAMIDES OF DIBASIC ACIDS Roy Herman Kienle andChester Alliert Amick,

Bound Brook,.N. J., asslgnors'to American yanamid Company, New York, N. Y,., a corporation of Maine No Drawing. Application July 1, 1943,

a Serial No. 493,135

11 Claims. (Cl. 8-70) I This invention relates to a new type of dyeing and printing assistant, dye compositions containing these assistants and products printed therefrom.

Use of printing-color pastes containing dyes,

particularly in printing operations using vat dyes, is sufficiently well-known so that the procedure has become almost standardized. The actual color source may be either a dye paste or a dye powder. In addition to the real color, a dyepaste usually contains agents to prevent drying out, settling and/or freezing. Dye powders, not being subject to these difficulties, do not require these agents butthey usually contain agents or are so processed as to promote dispersibility.

In either case, the dye paste or dye powder must be admixed with suitable thickener, usually a gum dispersion, to forma printing-color paste which is suitable for application. In the case of vat dyes, it is also necessary to add a reducing a ent and usually an alkali. Because the color yield from printing-color pastes often decreases rapidly as the paste ages after being made up,

these printing color pastes are'usually prepared I'heir addition at the proper point in the manufacture of the paste is not only easier, but in addition they are thus generally more uniformly dispersed throughouta printing-color paste made therefrom. As a result, the printing assistants usually operate more effectively when the printing-color paste is finally applied to the fabric.

It is only relatively recently that dye powders suitable for use in making up printing-color pastes have been available. Most of the printing aids previously used in dye pastes, beingeither liquid in form or extremely hydroscopic, can not be used with dye powders, thelatter being necessarily limited to the use of dry solids. Nevertheless, it is desirable that printing assistants be incorporated in the powders at the time of manufacture for the same reasons which apply in the case of dye pastes. A

Dye ==pastes containing various liquid printing assistants have been made. Among the liquid materials used are the alkylol amines, for example, triethanol amine; and/or polyhydric alcohols such as glycerine, glycol, diethyleneglycol and the like. Various derivatives therefrom also have been tried. If a printing aid is to be incorporated in a dye powder, a solid printing aid is necessary.

' Examples of such solids which'have been used rinsed and finally dried. Usually in processing textiles; the printed fabric also is soaped at or near the boil with about a 0.1% soap solution and again rinsed before the final drying operation,

1 In making up and applying printing-color pastes-it has been found that a material suitable for use as a printing assistant is of advantage in obtaining maximum color yield. The exact way in which these materials act to produce an improved color yield in printing is not entirely understood. It is with these printing aids or assistants that the present invention is particularly concerned. Y

Although printing aids are desirable in the printing-color pastes, the exact point at which in the past include the hydrochlorides of alkylol amines; silver salt (sodium anthraquinone betasulfonate); anthraquinone and certain. metal salts such as those of cobalt and iron. v

Unfortunately, most of these printing aids pre-' viously used are not as satisfactory as may be desired, Many of them will not in all cases pro- I verse effect on others, even to the extent of visibly It is preferable, however, that the printing assistant beincorporated in the-actual dye paste.-

altering the shade. None of them are suitable without modification for use both in paste and powder compositions.

There remains, therefore, a demand for suitable printing assistants which will producea satisfactory color intensification and will not cause deterioration of the dyeing or printing composition on standing. Preferably also, the assistants should be useful both withdye pastes and dye powders and in addition should be readily avail-. able or cheaply and easily prepared. It is, there-v fore, the object of the present inventipnto mvide a new type of printing assistant which possesses these desirable properties.

In general the object of the present invention is accomplished by using as a printing assistant one or more of the mixed diamides of dicarboxylic acids represented by this type formula in which Ac represents the residue of acyclic or aliphatic dibasic acid, Q represents a quinonyl group and R represents the residue of an alkyl,

aryl or alkaryl group. Typical of the mixed.

amides suitable for use according to the present invention is the N(alpha anthraquinonyl) N (ethanol) diamide of fumaric acid which has the probable formula so far as the present invention is concerned the' assistants may be added to the printing-color pastes at any point. They may be incorporated into the thickener; into the dye pastes or powders or may be blended directly into the printingcolor paste. However, as pointed out above, it

pensions. They have, therefore, a general application in both dye pastes and dye powders. They do not cause deterioration of printing-color pastes on standing. They encourage the production of excellent color yields even under hot ageing conditions. Their use is simple since they may be employed as powders, as suspensions in water or alcohol, producing excellent color yields whatever the mode of admixture.

In'preparing the compounds to be used as the printing assistants of the present inventionthe dicarboxylic acid may be quite widely varied. The compounds may be derived from either cyclic or aliphatic dicarboxylic acids. Of the cyclic carboxylic acids, phthalic acid is perhaps the most common and its derivatives have been found to give good results when used according to the present invention. The invention however is not meant to be so limited but includes derivatives of such acids as isophthalic, terephthalic, polyhydrophthalic, 'endoalkylenepolyhydrophthalic acids such as endomethylene tetrahydrophthalic,

endoethylene hexahydrophthalic and the like, and

the naphthalic acids as well as substituted acids derived therefrom.

Where derivatives of aliphatic dicarboxylic acids are used. the original acid or anhydride may be varied over a considerable range. If the- COOH or anhydride mo 0 v 040 a in the used the anhydride, 1/ may" have substantially any value from zero as in the case of oxalic acid to about eight without departing from the scope of the present invention. However, where y-is greater than about six, trouble is encountered in preparing the derivatives. Above about y=8, there is a tendency for the compounds to be too insoluble for satisfactory use. The acids may be either saturated acids such as malonic, succinic, glutaric, adipic, azelic, sebacic, and the like or unsaturated suchflas maleic, fumaric, and the like.

As pointed out in connection with the generic formula, Q represents a quinonyl group such as those of the naphthoquinones and anthraquinones. Paraquinonyl derivatives such as those from alpha-naphthoquinone and p-anthraquinone were found to give particularly good results according to the present invention. The invention however is not necessarily so limited. Similarly good results were obtained, for example, from the derivatives of beta-naphthoquinone and beta-anthraquinone.

In preparing the printing assistants of the present invention R also may be quite widely varied without departing from the intended scope. In general, the group may represent the residue after amidation of a wide range of alkyl, aryl or alkaryl amines. Of

.the aliphatic amines which were found to give excellent results according to the present invention, good examples are the primary and secondary alkyl amines and hydroxy amines such as' primary ethyl amine, ethanol amine, ethylene diamine, propylene diamine, butylamine and the like. Where the aliphatic group contains more than about five or six carbon atoms trouble is encountered in that the diamides tend to be too insoluble. There is also some tendency toward polymerization.

As pointed out, however, limited to the use of aliphatic amines. Aryl amines such as aniline, diphenylamine, the alphaand beta-naphthylamines and the like produce excellent printing assistants. Similar results are also obtained using mixed diamides of a dicarboxylic acid, a quinonyl amine and such alkarylamines as the toluidines, xylidines and the like.

Theoretically, R and Q may both be the same or different quinonyl radicals or the same or different residues of other amines. However, the present case is not intended to extend to such a scope. The specific case where both (-NH-R) and Q are similar quinonyl groups is set forth in our copending application for U. S, Letters Patent, Serial No. 493,134, filed of even date, and the case where (NH--R) and Q are the residuesof the same or different amines, neither being a quinonyl group, is covered in our copending application for U. S. Letters Patent, Serial No. 493,136,'flled of even date. 7

In preparing the compounds to be used in the present invention one feature should be noted.

The diamides may be prepared from a' monoquinonyl amide byreaction of the latter with another amine, forming thediamide by the elimination ofa second molecule of water. Heat is the invention is not.

asvmoa requiredtocarryoutthisreactiontoiorniatrue diamide. However, a compound which may be designated as a salt ordinarily forms on treating a monoquinonyl amide of a dicarboxylic acid with a second amine at a low temperature. These salts are also useful in carryingv out the teachings of the present invention but .are not intended to be within the scope of the present cceding examples this mixture is referred to as application, being set forth specifically in our copending application forU. 8. Letters Patent, Serial No. 493,130 filed of even date.

While the dye and printing paste compositions of the present invention are not limited to the use of any particular dyes or dye forms, they are especially suitable for use with vat-dyes in either paste or powder form. Particularly good results may be obtained using .the vat-dye powders of high autodispersibility set forth in Crossley et al., United States Reissue Patent .No. 21,402, reissued March 19, 1940. Bycomb the color materials of that patent intoprinting-paste compositions containing the printingassistants of the present invention, the full advantages of both may be gained with a resultant simplicity in use and excellence of shade and sharpness of color.

Printing pastes made in this way have the particular advantage that the dyes reinain in a highly dispersed'state as individual particles rather than as dispersions of particle aggregates. In the present specification and claims, where highly-dispersed dyes are referred to, reference to pastes in which the dye particles are so dispersed is intended. V a g The invention will be more fully set forth in connection with r the following exampleswhich are intended to be illustrative and not by way of limitation. All parts are by weight unless otherwise noted.

In the succeeding examples, test prints were made on two diiferent fabrics. referred to, a titanium-dioxide-pigmented, allviscose-rayomfiat-nepe was used. The cotton fabric referred to is an 80 x 80 bleached, unmer cerized, cotton print-cloth. Ageing of the prints thickener A. y

. Example 2 'l20parts of 3-2 British gum and 720 parts of KAC-4 gum (Stein Hall) were added to 5,000 parts of water andheated over a steam bath for. approximately 1 hours after the temperature reached 185-190 F. The source of heat was then removed but stirring was continued until the temperature decreased to 120 F. at which time 1,200 parts of potassium carbonate which had been previously dissolved in 1,000 parts of water was added to the cooked gum. 1,560 parts of sodium sulfoxylate formaldehyde were dis,- solved in 1,500 parts of water at a temperature of about 140 F; and added to the common mixture with stirring until the whole was thoroughly mixed. Finally, 360 parts of glycerine were. added and after thorough stirring the whole was bulked to 12,000 parts. 'In the succeeding examples this mixture is referred to as thickener B.

Example 3 a printed on rayon and cotton. The printed pieces were then dried in a hot-air dryer at alow temperature and aged in a steam age-r. Afterageing, the pieces were oxidized, soaped at-the boil Where rayon is 40 was carried outin a steam ager which was constructed in such a manner that controlled temperatures could be used. The temperature range normally used was 105 C. Those ageings referred to as plant or hot ageings were carried out in the temperature range of about 106-l10 C. In the case of the cotton prints ageing periods of 3 minutes, 5 minutes or both were used. on rayon, ageing periods of 5 and 10 minutes or tapioca. flour and 500 parts of cornstarch-were added to 2,500 parts of water and heated over a steam bath for approximately 1 hours after the temperature reached about 185 F. The

' source of heat was then removed but stirring was continueduntil the temperature decreased for 5 minutes in a 0.1% soap solution, again rinsed and finally ironed dry. Prints obtained from the paste containing the mixed amide-gave stronger color yields than those prints made from the control sample. This was particularly nounder plant ageing conditions. I Example 4 The procedure of Example 3 was duplicated except that 10 parts of Golden Orange G powder .ticeable with the cotton print cloth when aged (C. I.--1096), containing about 1.9 parts of real (we was used. The prints obtained from the paste containing the mixed amide were appreciably stronger than those obtained from the paste containing water only. both were used. The shortest period which gives Example 5 on diamide of Example 3 and 13.4 parts of water.

To this mixture was added 80 parts of thickener A. A second 8 parts of the Orange R powderto F. at which time 2,100 parts of potassium carbonate which had been previously dissolved in hotwater was added to the cooked gum. 1,100

parts of sodium sulfoxylate formaldehyde were I added to the common mixture at a temperature of about F. Subsequently, 1,400 parts oi. glycerine were added and after'thorough stirring the whole was bulked to about 10,000 parts. The mixture was cooled and stirred continuously until the mass reached room temperature. In the sucwas pasted with 14. parts of water and blended with 80 parts of thickener A. Each of these pastes were printed on rayon in the usual manner. The prints made from the paste containms the mixed diamide of maleic acid were deflnitely superior to those made from the printing paste containing no assistant.

, Example 6 'maric acid diamide was used as the printing assistant. The print; obtained'from the paste con- I and brighter.

taining the mixed amide gave very definitely stronger and brighter color values than those obtained from the paste containing water only.

Example 7 A sample of Vat Orange R wet presscake (C. I.121'7) was dispersed with the sodium salt f or disulfodinaphthyl methane and adjusted with water to contain about 12% real dye.

parts of this slurry were mixed with 0.3 part of N ethanol-N (beta-naphthoquinonyl) maleic acid The procedure of Example 7 was duplicated except that N (beta-anthraquinonyl) N (alphanaphthyl) maleic acid diamide was used in place of the beta-naphthyl product of the preceding example. The prints obtained from the paste containing the printing assistant were definitely stronger and brighter than those obtained from the pastes containing wateronly.

Example 9 The procedure of Example '7 was followed exactly. except that maleic acid diamide was replaced by the N(beta-anthraquinonyl) N ethanol succinic acid diamide. The color values obtained from this assistant were also definitely superior to those obtained from the printing pastes in which it was omitted.

Example 10 Another set of comparative pastes were prepared according to Example 7 except that N(betaanthraquinonyl) N ethanol phthalic acid diamide was used as a printing assistant. Again the color values obtained from the'paste containing the printing assistant were much stronger Example 11 The procedure of Example 7 was repeated using N(alpha-anthraquinonyl) N ethanol maleic acid diamide instead or N(beta-naphthoquinonyl) N ethanol diamide as the printing assistant. Both pastes were printed on cotton and rayon. The prints obtained from the paste containing the diamide of maleic acid were much stronger than those obtained from. the paste containing water only.

Example 12 N(alpha-anthraquinonyl) N ethanol iumari acid diamide was used as the printing assistant in the procedure of Example 7. from the paste containing the diamide again were stronger and brighter than those produced from the control paste.

Example 13 The procedure of Example 7 was repeated except that the N(alpha-anthraquinonyl) N (betaaminoethyl) diamide of succinic acid was used as the printing assistant. Prints on both cotton and rayon obtained irom the paste containing the printing assistant were stronger and brighter than those obtained from the paste in which the di amide was omitted.

Prints obtained Example 14 Pastes were prepared according to the procedure of Example '1 using no assistant in the control paste and N(alpha-anthraquinonyDN'(gammaaminopropyl) succinic acid diamide as an assistant in the other; Prints from the sample containing the assistant were stronger on both cotton and rayon than those obtained from the control paste.

' Example 15 The procedure of Example 7 was followed except that N(alpha-anthraquinonyl) N phenyl succinic acid diamide was used. Again, prints obtained on both cotton and rayon from the paste containing the printing assistant were definitely stronger and brighter than those obtained from the paste containing water only.

Example 17 Another set of comparative pastes were prepared according to Examples 7 and 16 using N(alpha-anthraquinonyl) N(p-tolyl) succinic acid diamide as the printing assistant. Similar printings on cotton and rayon had better color from the paste containing the printing assistant.

Example 18 The procedure of Example 17 was followed except that N(beta-anthraquinonyl) N'(metaxylyl) succinic acid diamide was used as the printing assistant. The color values obtained from this product were also definitely superior to those obtained when the printing pastes containing water only were used.

We claim:

1. A color composition comprising a vat dye and a dicarboxylic acid diamide represented by the formula Q-NH-Ac--NHR in which Ac represents the residue of a dicarboxylic acid selected from the group consisting of the phthalic acids, the naphthalic acids and the saturated and unsaturated aliphatic dicarboxylic acids of from 2 to 10 carbon atoms, Q represents a quinonyl radical selected from the group consisting oi the naphthoquinonyl and anthraquinonyl radicals, and R, represents the residue of an amine selected from the group consisting of the monoalkylamines and monoalkanolamines of from 1 to 8 carbon atoms, aniline, diphenyl amine, the mono-naphthylamines and their alkyl-substitilted derivatives.

2. A composition according to claim 1 in which the dye is a thio-indigo vat dye.

3. Avat dye powder composition comprising a powdered dye and a powdered dicarboxylic acid diamide represented by the formula Q--NHAc --NH---R in which .Ac represents the residue of a dicaracids or from 2.to 10 carbon atoms, Q represents 'tuted derivatives.

a quinonyl radical selected from the group consisting or thenaphthoquinonyl and anthraquinonyl radicals, and It .represents the residue of an amine selected from the group consisting of the monoalkylamines and monoalkanolamines of from 1 to 8carbon atoms, aniline, diphenyl amine, the mononaphthylamines and their alkyl substituted derivatives.

4. A dye composition comprising a vat dye powder of high autodispersibility and apowdered dicarboxylic acid diamide represented by the general formula Q-NH-Ac- NH-R in which Ac represents the residue of a dicarboxylic acid selected from the group consisting of the phthalic acids, the naphthalic acids and the saturated and unsaturated aliphatic dicarboxylic acids of from 2 to carbon atoms, Q represents a quinonyl radical selected iirom the group consisting of the naphthoquinonyl and anthraquinonyl radicals, and R represents the residue of an amine selected from the group consisting of the monoalkylamines and monoalkanolamines of from,1 to 8 carbon atoms, aniline, diphenyl amine,

the mono-naphthylamines and their alkyl-substi- 5. A color compositionaccordi ng to claim 1 in which Q represents a naphthoquinonyl group.

' 6. A color composition according to claim 1 in which Q represents an anthraquinonyl group.

7. A printing paste composition comprising a vat dye, a thickener and a dicarboxylic acid diamide represented by the general formula I Q-NH-.-Ac-NH-nv in which Ac represents the residue of a dicar-v I boxylic acid selected from the group consisting mononaphthylamines and their alkyl-substituted derivatives.

9. A printing paste composition comprising a highly-dispersed vat dye, a thickener and a dicarboxylic acid diamide represented by the general formula Q-NHAc-NH--R in which Ac represents the residue of a dicarboxylic acid selected from the group consisting of .the phthalic acids, the .naphthalic acids and the comprises printing a fabric with a printing paste composition comprising a vat dye, a thickener and a dicarboxylic acid diamide represented by the I general formula in which Ac represents the residue of a dicarboxylic acid selected from the group consisting of the phthalic acids, the naphthalic acids and the saturated and unsaturated aliphatic dicarboxylic acids of from 2 to 10 carbon atoms, Q represents-a of the phthalic acids, the naphthalic acids and,

the saturated and unsaturated aliphatic dicarboxylic acids of from 2 to 10 carbon atoms, Q represents a quinonyl radical selected from the group consisting of the naphthoquinonyl and anthra 'quinonyl radicals, and It represents the residue of an amine selected from the group consisting of the monoalkylamines and monoalkanolamines' of ouinonyl radical selected from the group consisting of the naphtho'quinonyl and anthraquinonyl radicals, and R represents the residue of an amine selected from the gfroupconsisting or the mono- -a1kylaniines and monoalkanolamines of from 1 to 8 carbon atoms, aniline, diphenyl amine, the

from 1 to 8 carbon atoms, aniline, diphenyl amine,

the mononaphthylamines and their alkyl-substistuted derivatives. v

8. A vat dye composition comprising a-vat dye,

resented by the general formula Q-NH-- Ac-NH R in which Ac represents the residue of a dicar- I boxylic acid selected from the group consisting of the phthalic acids, the naphthalic acids and the saturated and-unsaturated aliphatic dicarboxylic acids of from 2- to 10 carbon. atoms, Q represents a quinonyl radical selected from the group consisting of the naphthoquinoyland antraquinonyl radicals, and R presents'the residue of an amine .50 a thickener and a dicarboxylic acid diamide repmononaphthylamines and their alkyl-substituted derivatives.

11. An article of manufacture comprising a -fabric printed with a composition comprising avat dye and a dicarboxylic acid diamide represented by the general formula in which Ac represents the residueof a dicarboxylic acid selectedfrom the group consisting of the 'phthalic acids, the naphthalic acids and the satu rated and unsaturated aliphatic dicarboxylic acids offrom 2 tom carbon atoms, Q represents a quinonylradical selected from the group consisting of the naphthoquinonyl and anthraqulselected from the group consistingfof the mono-' 1 1 v alklylamine and monoalkanolamines of from 1 to Ilcarbon atoms, aniline,. diphenyl amine, the;

tuted derivatives. 1

nonylradicals. and R. represents the residue of an a amine selected from the group consisting of the monoalkylamines and monoalkanolamines of from 1 to 8 carbon atoms, aniline, diphenylaminc, the mononaphthylamines and their alkyl-subs ROY HERMAN mum cnns'nm g I 

